Patent GB-616247-A (GB)
Title: Manufacture of new amide derivatives
IPC: D06M13/402
Filed: 1944-03-21
Abstract: Salts of new amide derivatives are prepared by interacting an amide derived from a carboxylic acid containing at least 3 carbon atoms and having at least one amido-hydrogen atom, formaldehyde and a salt of ammonia or of a primary amine free from acid amide- or nitrile-groups, if desired, in the presence of a concentrated solution of a water-soluble carboxylic acid.  The amide may be reacted with formaldehyde to form the N-methylol compound by the usual methods, which are described, and then the latter reacted with the ammonium or amine salt.  Alternatively, the amide, formaldehyde and ammonium or amine salt are reacted together, suitably with heat in the presence of a solvent such as methanol, ethanol or acetone and, if desired, with the addition of a concentrated aqueous solution of a water-soluble carboxylic acid such as formic or acetic acid. Advantageously, more than one mole., for example 3 moles., of formaldehyde are used for each amide group.  The formaldehyde may be used in a polymeric form. As starting materials there may be used amides derived from aliphatic, aromatic or heterocyclic carboxylic acids such as propionic, acrylic, butyric, caprylic, lauric, palmitic, stearic, oleic, linoleic and adipic acids and coconut oil and hardened train oil fatty acids, benzoic, parastearylamino-benzoic, hexahydrobenzoic, naphthoic and tetrahydronaphthylacetic acids, resin or naphthenic acids such as abietic acid, chloromethylbenzoic and chloropropionic acids, N-substituted products of such amides such as N-methyl, N-ethyl, N-oxyethyl or N-dioxypropyl-lauric acid amide and phthalimide and diketopiperazine; ureas such as monophenyl-, monododecyl-, mono-octadecyl- and N : N1-didodecyl-ureas; urethanes such as octadecyl-urethane and methylene-dioctadecyl-urethane; hydrazides such as lauric acid hydrazide.  The ammonium salts include those of organic and inorganic acids such as the formate, acetate and chloride.  Specified salts of primary amines free from acid amide- or nitrile-groups include salts, for example acetates or formates, of aliphatic mono- or poly-amines such as methylamine, ethylamine, butylamines, amylamines, ethylene - diamine, diethylaminoethylamine, polyalkylene polyamines, oxyalkylamines such as monoethanolamine, oxypropyl- or oxybutylamines, aromatic mono- or polyamines such as aniline, para-dimethylamino-aniline, phenylene diamines and cycloaliphatic mono- or polyamines such as cyclohexylamine or hexahydro-o-phenylene diamine.  When salts of di-primary amines are used, 1 or 2 moles. of the amide may be used per mole. of amine salt. The products, for example in the form of their hydrochlorides or salts with water-soluble fatty acids, may be used as textile assistants.  The preferred products contain an aliphatic or cyclo-aliphatic residue of at least 12 carbon atoms and can be used as wetting, foaming, softening, dispersing or levelling agents or as agents for rendering fibres water-repellent (see Group VIII) or rendering dyeings resistant to water and for preventing agglomeration of cellulose fibres (see Group IV (c)). In examples: (1) ammonium acetate and stearic acid amide in glacial acetic acid are reacted with paraformaldehyde, the acetic acid then distilled off in vacuo, the residue treated with aqueous caustic soda and the resulting base converted into the soluble formate; the formate (and the mineral acid salts) decompose on heating and water-in-soluble products are precipitated; (2) in like manner, ammonium acetate and paraformaldehyde are reacted with coconut oil fatty acid methylolamide or stearic acid methylolamide; (3) methylamine acetate and stearic acid methylolamide in glacial acetic acid are reacted with paraformaldehyde, the base being isolated as in (1); it is soluble in dilute formic or acetic acid; the amide may be replaced by oleic acid methylolamide and the amine by ethylamine, allylamine or butylamine; in similar manner, (4)-(8) stearic acid methylolamide and o-phenylene diamine, ethylene diamine, ethanolamine, cyclohexylamine and p-aminodimethylaniline, respectively; (9) coconut oil fatty acid hydrazide and methylamine; (10) 4-nitro-methylol benzamide and methylamine; and (11) stearic acid methylamide and methylamine are reacted in excess glacial acetic acid with paraformaldehyde and the resulting salts converted into the bases.  The Specification as open to inspection under Sect. 91 includes the use of any primary amine salt and of amides of sulphonic acids in the above process.  It is also stated that the reaction may be carried out in the presence of any acid, including hydrogen chloride.  This subject-matter does not appear in the Specification as accepted.ALSO:Salts of new amide derivatives prepared by interacting an amide derived from a carboxylic acid containing at least 3 carbon atoms and having at least one amido-hydrogen atom, formaldehyde and a salt of ammonia or of a primary amine free from acid amide- or nitrile-groups, if desired, in the presence of a concentrated solution of a water-soluble carboxylic acid (see Group IV (b)), may be used, in the form of their hydrochlorides or salts with water-soluble fatty acids, as textile assistants, while the preferred products which contain an aliphatic or cycloaliphatic residue of at least 12 carbon atoms can be used as wetting, foaming, softening, dispersing or levelling agents or as agents for rendering fibres water-repellent (see Group VIII) or rendering dyeings resistant to water and for preventing agglomeration of cellulose fibrils.  In examples the following preparations are described: (1) ammonium acetate and stearic acid amide in glacial acetic acid are reacted with paraformaldehyde, the acetic acid then distilled off in vacuo; the residue treated with aqueous caustic soda and the resulting base converted into the soluble formate; (2) in like manner, ammonium acetate and paraformaldehyde are reacted with coconut oil fatty acid methylolamide or stearic acid methylol amide; (3) methylamine acetate and stearic acid methylol amide in glacial acetic acid are reacted with paraformaldehyde, the base being isolated as in (1): it is soluble in dilute formic or acetic acid yielding foaming solutions and precipitates dyestuffs containing sulpho-groups from their solutions; the amide may be replaced by oleic acid methylolamide and the amine by ethylamine, allylamine or butylamine; in similar manner; (4)-(8) stearic acid methylolamide and o-phenylene diamine, ethylene diamine, ethanolamine, cyclohexylamine and p-aminodimethylaniline, respectively; (9) coconut oil fatty acid hydrazide and methylamine; (10) 4-nitro-methylol benzamide and methylamine; and (11) stearic acid methylamide and methylamine are reacted in excess glacial acetic acid with paraformaldehyde; (12) artificial silk yarn is softened by treating with an aqueous solution of the acetate of the above-mentioned product derived from ethylene diamine.  Numerous additional starting materials are given, including aliphatic, aromatic and heterocyclic carboxy-amides, ureas, urethanes and hydrazides, and inorganic and organic salts of amines such as aliphatic mono- and poly-amines, oxyalkylamines and cycloaliphatic and aromatic mono- and polyamines.  The Specification as open to inspection under Sect. 91 includes the use of any primary amine salt and of amides of sulphonic acids in the above process.  It is also stated that the reaction may be carried out in the presence of any acid, including hydrogen chloride.  This subject-matter does not appear in the Specification as accepted.